EP0144251A1 - Oxydation catalytique du propylène en acétate d'allyle - Google Patents
Oxydation catalytique du propylène en acétate d'allyle Download PDFInfo
- Publication number
- EP0144251A1 EP0144251A1 EP84308534A EP84308534A EP0144251A1 EP 0144251 A1 EP0144251 A1 EP 0144251A1 EP 84308534 A EP84308534 A EP 84308534A EP 84308534 A EP84308534 A EP 84308534A EP 0144251 A1 EP0144251 A1 EP 0144251A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- propylene
- oxygen
- activated
- allyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 52
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims description 17
- 230000003647 oxidation Effects 0.000 title claims description 14
- 230000003197 catalytic effect Effects 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 150000001336 alkenes Chemical class 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002940 palladium Chemical class 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- -1 acetate anhydride Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000007791 liquid phase Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 13
- 229960000583 acetic acid Drugs 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 101000698125 Avena sativa Avenin-A Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
Definitions
- This invention relates to a.process for the oxidation of propylene to form allyl acetate,'a specialty chemical useful as a precursor to allyl alcohol and other articles of commerce. More particularly, this process is directed to the improvement of oxidizing propylene in one step in the presence of acetic acid to form allyl acetate at high selectivities and yields under moderate reaction conditions in the liquid phase by the use of a novel olefin-activated palladium catalyst.
- Typical soluble palladium and copper chloride and acetate catalyst systems give very poor allyl acetate selectivity when used in acetic acid in the presence of acetate ion (Clark, Hayden and Smith, Discuss. Faraday Soc., 46, 98 (1968)).
- Another type of catalyst, palladium trifluoroacetate operates under mild conditions in the liquid phase to give allyl acetate as the predominant product (French Patent 79-05874 (1980)) but catalyst recovery for re-use is difficult.
- allyl acetate has been prepared by heterogeneous catalysts in the vapor phase at high temperature or by a soluble catalyst in the liquid phase at low temperature. In the former case reaction selectivity is a problem and in the latter case both selectivity and catalyst recovery are major difficulties.
- propylene can be oxidized with air or oxygen in the presence of acetic acid in a single step in the liquid phase and under mild reaction conditions to form allyl acetate in high yield and at high selectivities when there is employed an activated palladium metal catalyst supported on carbon or alumina, wherein the palladium has been activated with a C 3 -C 6 olefin, preferably propylene prior to said oxidation under conditions described in detail below.
- the reaction in order to increase the reaction rate and at the same time reduce the reactor volume, it has been found to be advantageous that the reaction be carried out in a trickle bed reactor in which the liquid reaction medium is allowed to pass downward over a fixed catalyst bed and the allyl acetate product recovered at the bottom.
- the oxidation reaction can be carried out using an ebulating bed of catalyst while circulating gases and solvent.
- the catalyst employed in this invention may be prepared by activating a carbon- or alumina-supported palladium metal catalyst with a C3 C6 olefin, preferably propylene.
- the starting material from which the catalyst is prepared may be any finely divided palladium in the metallic state, on a support such as carbon or, less preferred, alumina, as for example a commercially available 5%, 10%, or 20% palladium on carbon available from standard catalyst manufacturers such as Engelhard Industries or Johnson Mathey, Inc.
- palladium metal catalyst or “palladium in the metallic state” is meant those palladium catalysts which have been prepared from their salts by known reduction means either commercially or as shown, for example, by Scharfe et al, U.S. Patent 3,970,713, or Holzrichter et al, U.S. Patent 3,275,680, but which have subsequently been exposed to the atmosphere in normal process procedures. While applicants do not wish to be bound by any particular theories, it is believed that in the normal course of handling and using the reduced catalysts of the prior art subsequent to reduction of the palladium, a certain proportion of the palladium surface species, by virtue of exposure to the atmosphere, becomes oxidized.
- this activation treatment be carried out at temperatures of at least about 60°C, up to 150°C, preferably about 65 to 95°C, for a period of at least about 10 minutes to about 120 minutes, preferably at least about 30 to 60 minutes, under oxygen-free conditions as described below. This is generally carried out at pressures of at least about 1 atmosphere, up to about 100 atmospheres of propylene, although about 2-20 atmospheres is preferred.
- activated palladium metal catalyst is meant, for purposes of this invention, a catalyst prepared in accordance with the above method.
- the activation be carried out in the substantial absence of oxygen, and preferably under essentially oxygen-free conditions. While the presence of small amounts of oxygen, to an extent which can be readily determined by those skilled in the art, can still result in a catalyst which performs under somewhat more mild conditions than the commercial catalysts described above, the full benefits of the present invention are derived from activating the catalyst under conditions which are as oxygen-free as can be obtained, at least within the standards of commercial feasibility.
- oxygen-free conditions can be achieved by known means, for example by using deaerated water or solvent, and pure olefin gas, during the activation of the catalyst.
- Deaeration can be readily achieved by placing the liquid under vacuum until it boils, or by bubbling the desired olefin through the liquid for a period of time until no more oxygen is displaced.
- the pure olefin can be obtained commercially in various grades such as chemical purity grade, research purity grade, or polymer grade, the latter two being preferred because of their higher purity of over about 99.7%. (The latter two are available, for example from Matheson, Division of Searle Medical Products, and Sun Co., respectively.)
- the catalyst of the invention may be prepared separately and maintained in an active state if kept in an oxygen-free atmosphere, more conveniently the preparation is carried out in the same reactor used for the propylene oxidation. This may conveniently be achieved, for example by adding a commercially available finely divided palladium on activated carbon to an acetic acid medium in a sealed reactor, flushing the system with propylene gas, and then heating the mixture under propylene pressure until the desired temperature for preparation of the catalyst is reached, at which time the mixture is stirred for at least 30 minutes at that temperature, again, in the absence of oxygen, and desirably in the presence of a slight excess of propylene.
- the propylene may be replaced by a mixture of propylene and oxygen, desirably with oxygen being present in approximately stoichiometric amounts to avoid deactivation of the catalyst, and the oxidation reaction carried out in the presence of acetic acid at pressures of from about 1 to 10 atmospheres.
- the pressure may be maintained by the further addition of the gas mixture from time to time until the desired propylene conversion to allyl acetate is achieved.
- Air may be used in place of oxygen, in which case the amount of propylene must be adjusted proportionately.
- the activating agent for the catalyst is preferably propylene, if desired there may instead be employed other light olefins having an allylic hydrogen and containing from 3-6 carbon atoms. Most preferred, in addition to propylene, are butene-1, butene-2 or isobutylene.
- the olefin-activated catalyst maintains its activity over long periods of time as long as at least small amounts of an acceptable olefin are present.
- it has been found beneficial to run the reaction by constantly sparging the propylene/oxygen or air reaction mixture through the acetic acid solution. In this way, the propylene is kept in excess and the catalyst remains highly active, thereby maintaining high selectivities and other advantages noted above.
- the ration of catalyst to reaction medium is desirably in the range of about 0.05-5.0 gram atoms of palladium per liter of reactant, and preferably about 0.1-1.0 gram atoms.
- the reaction can be conducted effectively by varying the volume of reactants and contact time with the catalyst in a generally known manner to achieve the high yields and selectivities disclosed herein.
- a metal acetate such as sodium acetate may be added to the reaction in amounts of up to 0.7 moles per liter of liquid medium for the purpose of enhancing the acetate ion concentration, and also the yield.
- the ratio of catalyst to reaction medium is desirably in the range of about 0.05-5.0 gram atoms of palladium per liter of solution, and preferably about 0.1-1.0 gram atoms.
- the reaction can be conducted effectively by varying the volume of reactants and contact time with the catalyst in a generally known manner to achieve the high yields and selectivities disclosed herein.
- the table compares activated palladium-on-carbon with standard soluble Pd(OAc) 2/ C U CI 2 catalysts.
- Examples 1 and 2 show that standard soluble palladium catalysts give poor selectivity to allyl acetate under the reaction conditions of this invention.
- Examples 3 and 4 show low yields and selectivities using palladium-on-carbon which had not been pre-reduced.
- Examples 6-9 show high yields of allyl acetate over activated catalysts which improve by increasing the added sodium acetate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55914083A | 1983-12-07 | 1983-12-07 | |
| US559140 | 1983-12-07 | ||
| US66456584A | 1984-10-29 | 1984-10-29 | |
| US664565 | 1984-10-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0144251A1 true EP0144251A1 (fr) | 1985-06-12 |
| EP0144251B1 EP0144251B1 (fr) | 1990-04-18 |
Family
ID=27071968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84308534A Expired - Lifetime EP0144251B1 (fr) | 1983-12-07 | 1984-12-07 | Oxydation catalytique du propylène en acétate d'allyle |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0144251B1 (fr) |
| CA (1) | CA1237146A (fr) |
| DE (1) | DE3481983D1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002083299A3 (fr) * | 2001-04-12 | 2003-02-27 | Celanese Int Corp | Catalyseur a base de palladium et procedes d'utilisation correspondants |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093559A (en) * | 1975-03-04 | 1978-06-06 | Hoechst Aktiengesellschaft | Process for the preparation of a palladium catalyst |
| US4133962A (en) * | 1975-02-14 | 1979-01-09 | Hoechst Aktiengesellschaft | Process for the preparation of carboxylic acid alkenyl esters |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH545259A (de) * | 1969-07-02 | 1973-12-15 | Bayer Ag | Verfahren zur Herstellung von Allylalkohol |
-
1984
- 1984-11-13 CA CA000467568A patent/CA1237146A/fr not_active Expired
- 1984-12-07 EP EP84308534A patent/EP0144251B1/fr not_active Expired - Lifetime
- 1984-12-07 DE DE8484308534T patent/DE3481983D1/de not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133962A (en) * | 1975-02-14 | 1979-01-09 | Hoechst Aktiengesellschaft | Process for the preparation of carboxylic acid alkenyl esters |
| US4093559A (en) * | 1975-03-04 | 1978-06-06 | Hoechst Aktiengesellschaft | Process for the preparation of a palladium catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002083299A3 (fr) * | 2001-04-12 | 2003-02-27 | Celanese Int Corp | Catalyseur a base de palladium et procedes d'utilisation correspondants |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3481983D1 (de) | 1990-05-23 |
| CA1237146A (fr) | 1988-05-24 |
| EP0144251B1 (fr) | 1990-04-18 |
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